Reforming catalysts



Nov. 4, 1958 C. N. KIMBERLIN, JR., ETAL REFORMING CATALYSTS Filed July 28, 1953 AIORPHUUS ALUIIIIA F!G.l

couzncm FIG. 2 CRYSTALLIIIE ALUIIIIA FIG. 3

6 "12w u IA x T svsmms Aumm 4 s k A 2 a I "0 I0 20 so 40 so so 10 so 90 mo DIFFRAOTION INTENSITY, ARBITRARY lIlllTS Oil-FRACTION ANGLE, DEGREES (2 9 CHARLES NIKIMBERLINNJR. INVENTORS ELROY M.GI ADROW retested Nov. 4, was

orbeta alumina trihydrate. These methods always yield end products that are crystalline materials- The par- 2859'185 ticular crystalline modification of the end product dependent upon the source of the material andupon the. REFORMING CATALYSTS particular-heat treatment applied thereto. It has been re- Charles N. Kimberlin Jr. and Eh'o M. Gladrow Baton d. m the hterature (Industna'l and l f t Rouge, La", assigno rs tb Esso Regearch and Erigineer- Charms/Ky page 8 (1950) there are mg Company, a corporation of Delaware sequences of phase transitions and the phase-changes that occur within a g1ven sequence follow a definite order Application y 1953, Serial 370,795 10 with increasing temperature of calcination. The initial alumina hydrate used as the raw material determines 14 Cimms' (CL 252-465) the particular sequence of phase transitions that that m'a-' ter'ial passes through. Transfer from. one sequence to another is difiicult to achieve. The phase transitions The present invention pertains to catalysts and par- 15 within a sequence by heating for one hour in dry air at inticularly to the prepartion of catalysts and/or catalyst creasing temperatures are as follows:

140 0. 280 0. 500 0. 1020 C. 1080 0: 1150 C. tritlilyrgte 200 0. mnillglilgme 450 0. 950 G. gamma 1050 C. kappa 11231 0. theta 1180 0. alpha.

140 0. 250 C. 800? 0. 11s0-0. tril i y di ate 'mon o li y rate eta 0 Q theta alpha Alpha 400 0. 850 0. l080 o. 1150 o. mmhydmte 450 G. gamma 1050o. delta 1120otheta 1200o. alpha I 400 0. mon iy rate 450 C. alpha supports for use in the reforming or hydroforming of It is the object of this invention to prepare improved lower boiling hydrocarbons or naphta fractions into motor hydroforming catalysts. fuels of excellentanti-knock and engine cleanliness It is also an object of this invention to prepare characteristics. 7 proved supports or carriers for various active catalytic Hydroforming is a wellknown process for treating substances. hydrocarbon fractions boiling within the motor fuel or It is a further object of this invention to prepare naphtha range to upgrade the same or increase the aromamorphous. alumina of high stability for use as a catalyst aticity and improve the engine cleanliness and anti-knock support; p characteristics of said fractions. It has been proposed These and other objects will appear more clearly from to'hydroform such lower boiling hydrocarbons by treating the detailed specification .and claims which follow. them in the presence of hydrogen or hydrogen-rich re- It has now been found that hydrolysis of. aluminum cycle gas (i. e. at relatively high hydrogen partial pres- 40 alcoholate in the presence of sulfur dioxide or of 5111- sures) at temperatures of about 7501050 F. and in confurous acid yields a non-crystalline or amorphous form tact with such catalysts as molybdenum oxide, chromium, of alumina. This can be accomplished in several ways: oxide or, in general, oxides and sulfides of metals of (1 by passing sulfur'dioxide through the aluminum alcogroups I-V-VHI- of the periodic system of elements, alone, holate followed by hydrolysis with steam or ambient air, or generally supported upon a base or spacing agent. (2) hydrolyzing the aluminum alcoholate in Wet alcohol Suitable" materials for thispurpose include activated containing dissolved sulfur dioxide, and ('3) effecting alumina, alumina gel, zinc aluminate spinel' or. the like. hydrolysis of aluminum alcoholate with an aqueous solu- It is well known in several catalytic hydrocarbon contion of sulfurous acid. After hydrolysis, the alumina" versions that catalysts having the same chemical composlurry is washed with water, or dilute solutions of amsition but prepared in diiferent ways may differ widely monia or ammonium salts, or it may be blown with steam' in their ability to promote certain reactions or hydroto substantially reduce the content of dissolved sulfur carbon conversions. Previous experience with hydrodioxide. The hydrolysis product is then dried in the forming catatlysts has shown that the catalyst base or conventional manner. Calcination of the dried materialsupport exerts a strong influence upon the ultimate beat 1200 F. for 6 hours gives a material which is essenhavioror activity of the catalyst. tially amorphous. Anexamination of the surface prop- Alumina is undoubtedly the most Widely used support erties of this material shows a surface area of about for hydroforming catalysts not only those containing. 165 square meters per gram and a pore volume of about molybdenum oxide or other group VI' metal oxides as 0L40 cc. per gram. These values compare favorably-with the active catalyst component but also those containing those for alumina made by hydrolyzing aluminum alcosmall amounts of platinum or palladium as the active hol'ate in water alone, viz., 150 mF/g. surface areaand component. Various methods have been proposed and 0.40 cc.'/g'. pore volume. The latter material, however,

utilized for the preparation of alumina catalystsuppdrts such as reaction of an aluminum saltto give-aluminumis in theeta crystalline phase.

The amorphous character of the alumina produced in accordance with the present invention may be readily seen in the accompanying drawing in which .5 Fig. 1 is an X-ray difiraction photograph of amorphous v aluminum alcoholate solution in the proper amount to.

alumina produced in accordance with the present per liter during the hydrolysis operation. Thehydrolysis:

is conducted at nominally room temperature but because of the large amount of heat of reaction, cooling may be employed.

'In' the process for producing amorphous alumina in:

volying hydrolyzing aluminum alcoholate in an aqueous sulfurous acid solution, the sulfur dioxide content of the hydrolysis medium should be about 6 grams of S per liter or more Although the hydrolysis may be carried outflover'a Wide temperature range, provided the S0 concentration issuitably maintained, room temperature or temperatures of about 65 to 95 F., are preferred.

jAmor-phous alumina can also be prepared in the form i About ,1 ounce of mercuric chloride is used as a catalyst started, cooling is necessary. After the reaction is complete the solution ofa'luminum amylate is hydrolyzed by of'sphe'rical or microspheroidal particles by spraying the aluminum alcoholate into an atmosphere of S0 and maintaining the finely divided droplets dispersed in the S0 until gelationhas been effected. After gelation, the droplets are contacted with alcohol containing water or an aqueous sulfurous acid solution to effect hydrolysis to yield amorphous alumina microspheres.

During the course of the hydrolysis some of the S0 may be "oxidized by ambientair to'SO thus creating sulfate ion'in solution. Because the presence of relatively large amounts of sulfate in ahydroforming catalyst is objectionable, oxidation of the sulfur dioxide by air is undesirable. The oxidation of S0 to 80;, may be inhibited by excluding air or by adding small amounts- (about one gram per liter of solution), of negative catalysts such as glycerol, mannitol, sugar, 'and other'suitable polyhydric alcohols to the hydrolysis system.

Aluminas comprising a mixture of amorphous and crystalline formsresult. when an insufiicient amount of sulfur dioxide is present in the hydrolysis medium. The relative amounts of crystalline and non-crystalline material depends on the S0 concentration level.

The amorphous alumina prepared as described above may be composited with the active catalytic component I or components by impregnating the same with a solutionof a heat decomposable compound of the active component such as ammonium molybdate,,drying and calcining or finely divided M00 or a heat decomposable compound of the active component can be dry mixed with the amorphous alumina and the resultant mixture heated or calcined to distribute and fix the active compound upon the base or support. The amount of molybdenum compound added should be sufiicient to give a M00 content of the finished catalyst of from about 5 to 15 wt. percent, preferably about 10 wt. percent. Other known hydroforming and/ or aromatization'catalysts such as chromium oxide,in amounts of 10 to 40 wt. percent, platinum in amounts of 0.05 to 2.0 Wt. percent, or palladium 0.5 to 5.0 wt. percent can be incorporated on the amorphous alumina prepared in accordance with the present invention. v

When preparing a platinum-aluminacatalyst a platinum salt, such as platinum chloride, is dissolved in a non aqueous medium such as any alcohol although n-butanol I or Pentasol (mixed amyl'alcohol's) is preferred. Re-- sidualamounts of water in the alcoholic solution may be removed from the system by azeotropic distillation. The alcoholic solution of platinum chloride is mixed with the ultimately yield 0.05 to 2.0% Pt on A1 0 preferably 0.3 to 1.0%.

The next step involves the hydrolysis. of the alcoholic aluminum alcoholate-platinum chloride solution in either (a) aqueous sulfurous acid, or (b) an alcohol containing water (up to about 20% by volume) and sulfur dioxide. Either hydrolysis medium yields a slurry of amorphous alumina containing the platinum in a highly dispersed form. Subsequent drying of the slurry' and reduction of the platinum to metal by treatment with hydrogen at 750 to 1050 F. is accomplished by means well known in the art.

Further specifications of this invention are embodied in the several specific examples which follow.

Example I A solution of aluminum alcoholate is prepared as follows. Fifty-four pounds of aluminum metal in the form of turnings are dissolved in about 124 gallons of a 50/50 mixture of mixed amyl alcohols and petroleum naphtha boiling in the range of about 200 to 300 F.

for the reaction between aluminum and the amyl alcohol.

It is necessary to heat the mixture to start the reaction between the metal and the alcohol, but after the reaction is mixingwith a solution of water in amyl alcohol.

The solution of waterin amyl alcohol is made by add- 'ing 10 gallons of water to 60 gallons of amyl alcohol with stirring. Fifty gallons of the alcohol-rich layer,

which comprises about 9 volume percent water, are Withdrawn and placed in the hydrolysis vessel. Fifty gallons of the aluminum alcoholate solution are slowly added to the wet alcohol using constant stirring. An additional 50 gallons of water are then added to the slurry after hydrolysis is complete to separate the alcohol phase from the aqueous alumina slurry. The alcohol layer is Wifllr.

drawn and the alumina slurry blown with steam to remove finaltraces of alcohol; The alumina slurry is dried) ina stearn heated oven at about 250 F. The dried? aluminaisconverted into a hydroforming catalyst by pregnating with a solution of ammonium molybdate using 1 about 1 .35 pounds of ammonium .molybdate dissolved in 3 quarts of water for each 10 pounds of alumina. After impregnation the catalyst is re-dried at about 250 F. and

activated by heating for 6 hours at about 1200 F. This catalyst comprises about 10% molybdena and is desig-,

nated catalyst A.

v v '7 Example II Fifty-four pounds of aluminum metal are converted into aluminum alcoholate as described in Example I. The water saturated alcohol is also prepared as described above. Sulfur dioxide is bubbled through 50 gallons of the Wet alcohol until the concentration of S0 is about 0.37 ounces per gallon. The aluminum alcoholate solution is added slowly tothe SO -Water-alcohol mixture using rapid agitation. During hydrolysis additional S0 is, added to maintain the concentration. After hydrolysis is complete, about 50 gallons of water are added to the slurry to separate the alcohol phase from the aqueous alumina slurry. The alcohol layer is withdrawn and the alumina slurry is blown with steam to remove any sulfur The alumina slurry is driedin a steam heated oven at about 250, F. "The dried amorphous alumina is converted into a hydrodioxide residues and final traces of alcohol.

forming catalyst 'by impregnating with a solution ofammonium molybdate using about 1.35 pounds of ammo-. nium molybdate dissolved in 3 quarts of water for each 10 pounds of alumina. After. impregnation, the catalyst is re-dried at about 250 F; and activated by heatingfor 6.hours at l200 F. This catalyst comprises about 10% molybdena and is *designated'catalyst B.

Catalysts-A and B described in Examples I and are employed in the form of inch x inch cylindrical pellets in a fixed catalyst bed operation for the hydroforming of a 200 Rte 330 F. boiling range virgin naphtha from mixed southeast and west Texas crudes. The aniline point of this naphtha is 126 The conditions employed are 900 F. temperature, 200 p. s. i. g. pressure, using 1500 cubic feet of feed hydrogen per barrel of naphtha feed, and a naphtha feed rate of approximately one volume of naphtha per volume of catalyst per hour; slight adjustments are made in the feed rate in order to obtain a C product with each catalyst having an aniline point of F. The yields of gas and C products are shown in the tabulation below.

Yield of Gas, Wt. percent Example IV Aluminum alcoholate is prepared as described in Example I. Twenty-fivegallons of water are charged to the hydrolysis vessel and sulfur dioxide added until the concentration of S0 is about 1.2 ounces per gallon of water. Twelvegallons of aluminum alcoholate are then added slowly to the aqueous sulfurous acid solution using rapid mixing to effect hydrolysis. The organic layer is withdrawn and residual amounts of alcohol and hydrocarbon are removed by blowing with steam. The aqueous .slurry of amorphous alumina 'is treated 'batchwise with 17 pounds of'hydroxyl form regenerated Amberlite IRA-400 anion exchange resin. Amberlite IRA-400 is a commercial anion exchange resin supplied by the Rohm and Haas Company of Philadelphia; this material is a strongly basic resin, believed to be based on polystyrene and containing quaternary ammonium groups. It is supplied in the form of the chloride salt and is converted to the hydroxyl form by treating with sodium hydroxide solution. About 5 volumes of this sodium hydroxide solution are used to convert 1 volume of wet resin to the hydroxyl form. After treatment with caustic the resin is washed with water to free it of soda. Other anion exchange resins may be used. After mixing the resin and slurry, the mixture is passed through a 40 mesh screen to separate the alumina slurry from the coarse resin particles. The alumina slurry is oven dried at 250 F. in the conventional manner. The dried amorphous alumina is converted into a hydroforming catalyst by impregnating with a solution of chloroplatinic acid using about 12.5 grams of platinum chloride (40% Pt) dissolved in about 0.8 liters of water for each kilogram of alumina. After impregnation this catalyst is redried at about 250 F. This catalyst comprise about 0.5% platinum.

A portion of the above platinum on amorphous alumina catalyst is heated for 64 hours at 1250 F. in air. An X-ray examination of the cooled material shows the alumina base to be still amorphous and, moreover, the average platinum crystal size is seen to be much less than 100 angstroms, showing the stabilizing action of amorphous A1 0 toward platinum crystal growth.

A portion of this catalyst is employed in the form of 7 inch x X inch cylindrical pellets in a fixed bed hydroforming operation for the hydroforming of a 200 F. to 330 F. boiling range virgin naphtha having a gravity of 54.4 API and a Research octane number of 58 (clear). The conditions employed are 925 F. bath temperature, 200 p. s. i. g. pressure, using about 6000 cubic feet of feed hydrogen per barrel of naphtha feed. The product from the hydroforming operation comprises a yield of about 6 90.5 volume percent C gasoline having an octane number of (Research clear).

Catalysts prepared upon amorphous alumina supports in accordance with the present invention can be used. for reforming or hydroforming hydrocarbon feed stocks in fixed bed, moving bed or fluidized solid type operations. The feed or charging stock may be a virgin naphtha, a cracked naphtha, a Fischer-Tropsch naphtha or the like, having a boiling range of from about to 430 F., or. it may be a narrow boiling cut from within this range. The feed stock is preheated alone, or, if desired, in admixture with hydrogen-rich gas to reaction temperature or to the maximum temperature possible while avoiding thermal degradation of the feed stock. Ordinarily, preheating of the feed stock is carried out to temperatures of about 800- 1050 F., preferably about 975 F. Thermal degradation at preheat temperatures can be avoided or minimized by limiting the time of residence of the feed stock in the preheat coils, transfer and-feed inlet lines.

Hydrogen-rich gas, preferably process or recycle gas containing from 40 to 70 or more volume percent hydro? gen is circulated through the reaction zone at a rate of from about 1000 to 8000 cu. ft. per barrel of naphtha feed. The recycle gas is preheated to temperaturesof about 1100-1200 F., preferably about 1185 F. before introduction into the reaction zone. The amount of recycle gas circulated is preferably the minimum amount that will suflice to carry the necessary heat of reaction into the reaction zone andkeep carbon formation at a satisfactory low level.

The reaction zone is maintained at a temperature between about 875 and 1500 F., preferably about 925 F. and at pressures between about 50 and500 lbs. per sq. inch, preferably about 200 lbs. per sq. inch. Regeneration of the catalyst is eifected by burning off carbonaceous deposits with air or oxygen-containing gas at, temperatures of about 11001200 F., ordinarily at essentially the same pressure as is maintained in the reaction zone or vessel. In fluidized solids systems, the average residence time of the catalyst particles in the reaction zone is from about 2 to 4 hours while the average residence time of the catalyst particles in the regenerator is of the order of from about 3 to 15 minutes.

The weight ratio of catalyst to oil introduced into the reactor should be about 0.5 to 1.5, preferably about 1.0. Space velocity or weight in pounds of feed charged per hour per pound of catalyst in the reactor depends upon the age or activity level of the catalyst, the character of the feed stock and the desired octane number of the product. Space velocity may vary, for example, from about 1.5 wt./hr./wt. to about 0.15 Wt./hr./wt.

The foregoing description contains a limited number of embodiments of the present invention. It will be understood, however, that numerous variations are possible without departing from the spirit or scope of this invention.

What is claimed is:

1. A method of preparing improved catalyst supports which comprises hydrolyzing an aluminum alcoholate in the presence of sulfur dioxide to form amorphous alumina, drying and calcining said amorphous alumina.

2. A method of preparing improved catalyst supports which comprises contacting aluminum alcoholate with sulfur dioxide to cause gelation of the alcoholate, hy-

' drolyzing the sulfur dioxide-containing alcoholate to form amorphous alumina, drying and calcining said amorphous alumina.

3. A method of preparing improved catalyst supports which comprises hydrolyzing an aluminum alcoholate in the presence of alcohol containing a minor proportion of water and sulfur dioxide to form amorphous alumina, drying and calcining said amorphous alumina.

4. A method of preparing improved catalyst supports which comprises hydrolyzing an aluminum alcoholate in an aqueous solution ofsulfurous acid to form amorphous alumina, drying and calcining the amorphous alumina. 5. A method of preparing improved catalyst supports which comprises hydrolyzing an aluminum alcoholate in an aqueous solution of sulfurous acid containing a compound selected from the group consisting of glycerol, mannitol and sugar inhibiting the oxidation of S to S0 drying and, calcining the amorphous alumina.

6. A method of preparing active reforming catalyst compositions which comprises hydrolyzing an aluminum alcoholate in the presence of sulfur dioxide to form amorphous alumina, heating said amorphous alumina toremove water therefrom, depositing an active reforming catalyst selected from the group consisting of platinum metals and group VI metal compounds on said amorphous alumina and-activating the resultant composition.

7. A method of preparing active reforming catalyst compositions which comprises contacting aluminum alcoholate with sulfur dioxide to cause gelation of the alcoholate, hydrolyzing the sulfur dioxide-containing alcoholate to form amorphous alumina, heating said amorphous allnnina to remove water therefrom, depositing an activereforming catalyst selected from the group consisting of platinum metals and group VI metal compounds on said amorphous alumina and activating the resultant composition.

-8. A method of preparing active reforming catalyst compositions which comprises hydrolyzing an aluminum alcoholate in the presence of alcohol containing a minor proportion of water and sulfur dioxide to form amorphous alumina, heating said amorphous alumina to remove water therefrom, depositing an active reforming catalyst selected from the group'consisting of platinum metals and group VI metal compounds on said amorphous alumina and activating the resultant composition.

9. A method of preparing active reforming catalyst compositions which comprises hydrolyzing an aluminum alcoholate in an aqueous solution of sulfurous acid to 8 form amorphous alumina, heating said amorphous alumina to remove water therefrom, depositing an active reforming catalyst selected from the group consisting of platinum metals and group VI metal compounds on said amorphousalumina and activating the resultant composition. v 1

10. A method of preparing active reforming catalyst compositions which comprises hydrolyzing an aluminum ,alcoholate in an aqueous solution of sulfurous acid. containing a compound selected from the group consisting of glycerol, mannitol and sugar inhibiting the oxidation of S0 to S0 to form amorphous alumina, heating, said amorphous alumina to remove water therefrom, depositing an activereforming catalyst selected from the group consisting of platinum metals and-group VI metal cornpounds on said amorphous alumina and activatingfthe resultant composition.

11. The process as defined in claim 6 wherein the active reforming catalyst is a group VI metal compound. 12.. The process as defined in claim 6 wherein the active reforming catalyst is 5.0 to 15 wt. percent molybdenum oxide.

13. The process as defined in claim 6 wherein the active reforming catalyst is a platinum .metal. 14. The process as defined in claim 6 wherein the active reforming catalyst is 0.05 to 2.0 wt. percent platinum.

References Cited in the file of this patent UNITED STATES PATENTS Archibald et al Oct. 12, 1943 2,331,292 2,479,109 Haensel Aug. 16, 1949 2,636,865 -Kimberlin Apr. 28, 19 53 FOREIGN PATENTS 498,510 Great Britain Jan. 2, 1939 667,145 Great Britain Feb. 27, 1952. 

1. A METHOD OF PREPARING IMPROVED CATALYST SUPPORTS WHICH COMPRISES HYDROLYZING AN ALUMINUM ALCOHOLATE IN THE PRESENCE OF SULFERR DIOXIDE TO FORM AMORPHOUS ALUMINA, DRYING AND CALCINING SAID AMORPHOUS ALUMINA.
 6. A METHOD OF PREPARING ACTIVE REFORMING CATALYST COMPOSITIONS WHICH COMPRISES HYDROLYZING AN ALUMINUM ALCOHOLATE IN THE PRESENCE OF SULFUR DIOXIDE TO FORM AMORPHOUS ALUMINA, HEATING SAID AMORPHOUS ALUMINA TO REMOVE WATER THEREFROM, DEPOSITING AN ACTIVE REFORMING CATALYST SELECTED FROM THE GROUP CONSISTING OF PLATINUM METALS AND GROUP VI METAL COMPOUNDS ON SAID AMORPHOUS ALUMINA AND ACTIVATING THE RESULTANT COMPOSITION. 